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Lu Z, Chang YC, Gao H, et al. Communication: direct measurements of nascent O((3)P0,1,2) fine-structure distributions and branching ratios of correlated spin-orbit resolved product channels CO(ã(3)Π; v) + O((3)P0,1,2) and CO(X̃(1)Σ(+); v) + O((3)P0,1,2) in VUV photodissociation of CO2. J Chem Phys. 2014;140(23):231101doi: 10.1063/1.4883515.
Lu, Z., Chang, Y. C., Gao, H., Benitez, Y., Song, Y., Ng, C. Y., & Jackson, W. M. (2014). Communication: direct measurements of nascent O((3)P0,1,2) fine-structure distributions and branching ratios of correlated spin-orbit resolved product channels CO(ã(3)Π; v) + O((3)P0,1,2) and CO(X̃(1)Σ(+); v) + O((3)P0,1,2) in VUV photodissociation of CO2. The Journal of chemical physics, 140(23), 231101. https://doi.org/10.1063/1.4883515
Lu, Zhou, et al. "Communication: direct measurements of nascent O((3)P0,1,2) fine-structure distributions and branching ratios of correlated spin-orbit resolved product channels CO(ã(3)Π; v) + O((3)P0,1,2) and CO(X̃(1)Σ(+); v) + O((3)P0,1,2) in VUV photodissociation of CO2." The Journal of chemical physics vol. 140,23 (2014): 231101. doi: https://doi.org/10.1063/1.4883515
Lu Z, Chang YC, Gao H, Benitez Y, Song Y, Ng CY, Jackson WM. Communication: direct measurements of nascent O((3)P0,1,2) fine-structure distributions and branching ratios of correlated spin-orbit resolved product channels CO(ã(3)Π; v) + O((3)P0,1,2) and CO(X̃(1)Σ(+); v) + O((3)P0,1,2) in VUV photodissociation of CO2. J Chem Phys. 2014 Jun 21;140(23):231101. doi: 10.1063/1.4883515. PMID: 24952514.
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J Chem Phys. 2014 Jun 21;140(23):231101. doi: 10.1063/1.4883515.

Communication: direct measurements of nascent O((3)P0,1,2) fine-structure distributions and branching ratios of correlated spin-orbit resolved product channels CO(ã(3)Π; v) + O((3)P0,1,2) and CO(X̃(1)Σ(+); v) + O((3)P0,1,2) in VUV photodissociation of CO2.

The Journal of chemical physics

Zhou Lu, Yih Chung Chang, Hong Gao, Yanice Benitez, Yu Song, C Y Ng, W M Jackson

Affiliations

  1. Department of Chemistry, University of California, Davis, Davis, California 95616, USA.

PMID: 24952514 DOI: 10.1063/1.4883515

Abstract

We present a generally applicable experimental method for the direct measurement of nascent spin-orbit state distributions of atomic photofragments based on the detection of vacuum ultraviolet (VUV)-excited autoionizing-Rydberg (VUV-EAR) states. The incorporation of this VUV-EAR method in the application of the newly established VUV-VUV laser velocity-map-imaging-photoion (VMI-PI) apparatus has made possible the branching ratio measurement for correlated spin-orbit state resolved product channels, CO(ã(3)Π; v) + O((3)P0,1,2) and CO(X̃(1)Σ(+); v) + O((3)P0,1,2), formed by VUV photoexcitation of CO2 to the 4s(10 (1)) Rydberg state at 97,955.7 cm(-1). The total kinetic energy release (TKER) spectra obtained from the O(+) VMI-PI images of O((3)P0,1,2) reveal the formation of correlated CO(ã(3)Π; v = 0-2) with well-resolved v = 0-2 vibrational bands. This observation shows that the dissociation of CO2 to form the spin-allowed CO(ã(3)Π; v = 0-2) + O((3)P0,1,2) channel has no potential energy barrier. The TKER spectra for the spin-forbidden CO(X̃(1)Σ(+); v) + O((3)P0,1,2) channel were found to exhibit broad profiles, indicative of the formation of a broad range of rovibrational states of CO(X̃(1)Σ(+)) with significant vibrational populations for v = 18-26. While the VMI-PI images for the CO(ã(3)Π; v = 0-2) + O((3)P0,1,2) channel are anisotropic, indicating that the predissociation of CO2 4s(10 (1)) occurs via a near linear configuration in a time scale shorter than the rotational period, the angular distributions for the CO(X̃(1)Σ(+); v) + O((3)P0,1,2) channel are close to isotropic, revealing a slower predissociation process, which possibly occurs on a triplet surface via an intersystem crossing mechanism.

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